Photographic processes using silver halide have been most widely used in the past due to their excellent photographic properties such as sensitivity or control of gradation, etc., as compared with other photographic processes, such as, an electrophotographic process or a diazo photographic process. In recent years, with respect to image formation processes for photographic materials using silver halide, many techniques capable of obtaining images with ease and rapidly have been developed by changing the conventional wet process using a developing solution into a dye process such as a process using heat, etc.
Heat-developable photographic materials are known in the field of these techniques, and heat-developable photographic materials and processes therefor have been described in U.S. Pat. Nos. 3,152,904, 3,301,678, 3,392,020 and 3,457,075, British Pat. Nos. 1,131,108 and 1,167,777, and Research Disclosure, No. 17029, pages 9 to 15 (June, 1978).
Many different processes for obtaining color images have been proposed. With respect to processes for forming color images by the reaction of an oxidation product of a developing agent with a coupler, it has been proposed to use a p-phenylenediamine type reducing agent and a phenolic coupler or an active methylene coupler as described in U.S. Pat. No. 3,531,286, a p-aminophenol type reducing agent as described in U.S. Pat. No. 3,761,270, a sulfonamidophenol type reducing agent as described in Belgian Pat. No. 802,519 and Research Disclosure, pages 31 and 32, (September, 1975) and the combination of a sulfonamidophenol type reducing agent and a 4-equivalent coupler as described in U.S. Pat. No. 4,021,240. These processes, however, are disadvantageous in that turbid color images are formed, because a reduced silver image and a color image are simultaneously formed on the exposed area after heat development. In order to eliminate these disadvantages, there have been proposed a process which comprises removing a silver image by liquid processing or a process which comprises transferring only the dye to another layer, for example, a sheet having an image receiving layer. However, the latter process is not desirable because it is not easy to transfer only the dye as distinguishable from unreacted substances.
Another process which comprises introducing a nitrogen containing heterocyclic group into a dye, forming a silver salt and releasing a dye by heat development has been described in Research Disclosure, No. 16966, pages 54 to 58 (May, 1978). According to this process, clear images cannot be obtained, because it is difficult to control the release of dyes from nonexposed areas, and thus it is not a conventional process.
Also, processes for forming a positive color image by a thermal silver dye bleach process, with useful dyes and methods for bleaching have been described, for example, in Research Disclosure, No. 14433, pages 30 to 32 (April, 1976), ibid., No. 15227, pages 14 and 15 (December, 1976) and U.S. Pat. No. 4,235,957.
However, this process requires an additional step and an additional material for accelerating bleaching of dyes, for example, heating with a superposed activating agent sheet. Furthermore, it has a drawback that the resulting color images are gradually reduced and bleached by coexisting free silver during preservation for a long period of time.
Moreover, a process for forming a color image utilizing a leuco dye has been described, for example, in U.S. Pat. Nos. 3,985,565 and 4,022,617. However, this process is not desirable because it is difficult to stably incorporate the leuco dye in the photographic material and coloration gradually occurs during preservation.
It is also known in the field of textiles to dye polyester with an azo dye. Although processes for application of the dyeing of polyester to a photographic field have been proposed, sufficiently desirable results have not been obtained. For example, a process for using a polyester film as an image recieving layer is described in U.S. Pat. No. 4,235,957. However, according to this process, the diffusion of dyes to a polyester film and the bleaching of dyes occurs simultaneously in order to form a positive image by a silver dye bleach process, and thus it is difficult to form an image with a good S/N value.
A process for transferring a dye formed upon the coupling reaction of a hydrazone developing agent with a coupler into a polyester support is described, for example, in British Pat. No. 2,056,103. However, this process does not provide a sufficient image since a dye forming efficiency of the coupling reaction is low and the transferring property to the support is poor.